WO2011011771A2 - Metal-free supported polycrystalline diamond (pcd) and method to form - Google Patents

Metal-free supported polycrystalline diamond (pcd) and method to form Download PDF

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Publication number
WO2011011771A2
WO2011011771A2 PCT/US2010/043197 US2010043197W WO2011011771A2 WO 2011011771 A2 WO2011011771 A2 WO 2011011771A2 US 2010043197 W US2010043197 W US 2010043197W WO 2011011771 A2 WO2011011771 A2 WO 2011011771A2
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WO
WIPO (PCT)
Prior art keywords
substrate
metal
cutting element
layer
carbide
Prior art date
Application number
PCT/US2010/043197
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English (en)
French (fr)
Other versions
WO2011011771A3 (en
Inventor
Steven W. Webb
Original Assignee
Diamond Innovations, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Diamond Innovations, Inc. filed Critical Diamond Innovations, Inc.
Priority to EP10738117.0A priority Critical patent/EP2456946B1/en
Priority to KR1020127004748A priority patent/KR101741282B1/ko
Priority to JP2012521870A priority patent/JP6038652B2/ja
Publication of WO2011011771A2 publication Critical patent/WO2011011771A2/en
Publication of WO2011011771A3 publication Critical patent/WO2011011771A3/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C26/00Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23CMILLING
    • B23C2222/00Materials of tools or workpieces composed of metals, alloys or metal matrices
    • B23C2222/28Details of hard metal, i.e. cemented carbide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23CMILLING
    • B23C2226/00Materials of tools or workpieces not comprising a metal
    • B23C2226/31Diamond
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C2204/00End product comprising different layers, coatings or parts of cermet

Definitions

  • Th ⁇ present disclosure relates to blanks having a layer of integrally bonded superabrasive particles supported on sintered carbide substrates and to the sectioning by ablation techniques of such blanks. More particularly, the present disclosure relates to the composition and structure of the substrate, where, upon ablation by, for example, a laser, the ablated material does not close the cut and the cut in the substrate is maintained opened.
  • PCD polycrystalline diamond
  • superabrasives are incorporated into drill bits for use in rock drilling and other operations which require high abrasion resistance or wear resistance.
  • U.S. Pat. Nos. 4,109,737 and 5,374,854 the disclosures of each of which are herein incorporated by reference in their entirety, describe drill bits with a tungsten carbide substrate having a polycrystalline diamond compact on the outer surface of the cutting element.
  • the superabrasive material forms a compact, which is a mass of diamond particles or cBN particles, bonded together to form an integral, tough, high-strength mass.
  • Diamond or cBN particles may be bonded together as a compact in a particle-to-particle self-bonded relationship, optionally with a bonding medium disposed between the particles, such as a catalyzing material used to bond the abrasive particles together.
  • a bonding medium disposed between the particles, such as a catalyzing material used to bond the abrasive particles together.
  • EDM electrical discharge machine
  • EDM is a slow process, with cutting rates of about 5 mm 2 /min through PCD and carbide, and is sensitive to the electrical conductivity, and spatial variation of electrical conductivity, of PCD and PCBN, which is not well controlled in synthesis.
  • EDM is, in practice, useless for non-conducting materials like ceramics. EDM produces miles of spent wire which must be disposed.
  • Another technique used to ablate or cut PCD or PCBN is laser cutting. This technique is currently gaining popularity due to very high cut rates, >250 mm2/min, potentially narrow kerf width, no consumables, high precision and reasonable cut edge quality for unsupported PCD and unsupported PCBN, where unsupported indicates there is no underlying substrate of hard material, such as cemented carbide.
  • a major issue with laser ablation cutting of supported PCD and supported PCBN is the recondensing or recasting of metal from the carbide support and PCD back into the kerf or along the cutting edge after the laser has passed.
  • gas is directed to the cutting area, but this is ineffective in removing the condensable metal vapor.
  • the metal content of carbide conventionally approximately 6-13 wt-% cobalt, results in considerable condensable metal fume being produced.
  • PCD contains about 5 to about 20% w/w Co metal, but since the carbide support is 10 times heavier than the PCD, the majority of metal vapor derives from the carbide support.
  • an exemplary cutting element comprises a substrate and a layer of polycrystalline diamond particles sintered to the substrate, the layer including a working surface at a first surface distal from the substrate, wherein the substrate is non-magnetic and electrically conductive.
  • An exemplary method of forming a cutting element comprises positioning a substrate on a first side of a layer of diamond particles, positioning a catalyst source on a second side of the layer of diamond particles, and sintering the substrate, the layer of diamond particles and the catalyst source at a pressure greater than about 20 kbar and a temperature greater than about 1200 5 C to form a layer of polycrystalline diamond particles bonded to the substrate, wherein the substrate is largely free of condensable material, non-magnetic and electrically conductive.
  • An exemplary method of forming a cutting element comprises a substrate and a layer of diamond particles blended with catalyst particles, the substrate and diamond-catalyst particles sintered at greater than about 20 kbar and greater than about 1200 Q C to forma a polycrystalline diamond bonded to the substrate, wherein the substrate, is non-magnetic, electrically conductive and is largely free of condensable material.
  • An exemplary method of sectioning a cutting element comprises ablating the cutting element to form a reduced shape, wherein the cutting element includes a substrate and a layer of polycrystalline diamond sintered to the substrate, and wherein the substrate is non-magnetic and electrically conductive.
  • FIG. 1 is a schematic cross-sectional representation of an exemplary cutting element.
  • FIG. 2 is an SEM micrograph at 10,00OX magnification of a surface of an exemplary embodiment of a substrate used to support a superhard material.
  • FIG. 3 is a diagram of one experimental variation in which the catalyst is supplied via a powder and the substrate is a combination of conventional and - metal-free carbide.
  • FIG. 4 is an image of the formed cutting element in Example 1 .
  • FIG. 5 is an image of a cross-section of the cutting element in Example 1 showing the cut surface where the substrate and layer have been sectioned by a laser.
  • FIG. 6 is a top-view image of the laser cut conventional carbide disk showing complete lack of separation.
  • FIG. 7 is a side-image of the cross section of the laser cut metal-free carbide, showing the clean separation and good edge quality.
  • FIG. 1 is a schematic cross-sectional representation of an exemplary cutting element.
  • the cutting element 10 comprises a substrate 12 and a layer 14 of superhard material, such as particles of diamond or of cubic boron nitride, sintered to the substrate 12. Sintering bonds the particles of the superhard material to each other as well as to the substrate, forming a layer of polycrystalline diamond particles (PCD) or a layer of polycrystalline cubic boron nitride (PCBN).
  • PCD polycrystalline diamond particles
  • PCBN polycrystalline cubic boron nitride
  • the layer 14 of the superhard material includes a first surface 16 distal from the substrate 12 that is a working surface of the cutting element 10, i.e., the surface, at least a portion of which, contacts geological formations or workpieces during drilling or cutting operations with the cutting element.
  • the first surface can be rectilinear or can be chamfered at one or more edges 18, as is known in the art.
  • the substrate 12 is non-magnetic, due to low or no metal or condensable material present, and is electrically conductive, due to the presence of
  • the substrate 12 substrate has a composition including tungsten carbide and an iron group binder metal present in an amount of less than about 0.5 wt-%, alternatively, greater than 0 wt-% to less than about 0.5 wt-%, greater than 0 wt-% to less than about 0.4 wt-%, or greater than 0 wt-% to less than about 02 wt-%.
  • the substrate composition is free of binder metal.
  • the composition of the substrate 12 can further optionally include a metal carbide, such as Mo 2 C.
  • FIG. 2 is an SEM micrograph at 10,00OX magnification of a surface of an exemplary embodiment of a substrate 12.
  • the micrograph in FIG. 2 shows a matrix having a composition of about 99 wt-% WC and porosity of less than about 3 vol-%.
  • the grains have an average diameter of about 1 micron.
  • the substrate can be incorporated into a cutting element in support of and bonded to a layer of superhard material.
  • An example of a bonding method is sintering.
  • a cutting element is formed by positioning a substrate on a first side of a layer of diamond particles.
  • a catalyst source is positioned on a second side of the layer of diamond particles, as a metal alloy foil or a cermet disk, or simply blended as powder with the diamond particles.
  • An example of a catalyst source is a material including an iron-group element.
  • the material for the catalyst source can be in any suitable form, such as powders, particles or a solid body, layer or film.
  • the substrate, the layer of diamond particles and the catalyst source are sintered at a pressure greater than about 20 kbar and a temperature greater than about 1200 Q C, also known as high pressure/high temperature (HPHT) processing (see, for example, U.S. Patent No. 5,512,235, the entire contents of which are incorporated herein by reference, for details on conventional HPHT processes and related equipment and consumables) to form a layer of HPHT processing (see, for example, U.S. Patent No. 5,512,235, the entire contents of which are incorporated herein by reference, for details on conventional HPHT processes and related equipment and consumables) to form a layer of HPHT
  • the substrate is non-magnetic and is electrically conductive.
  • the cutting element can be sectioned by any ablation technique.
  • a cutting element including a substrate and a layer of polycrystalline diamond sintered to the substrate, is sectioned by ablating the cutting element to form a reduced shape.
  • the substrate is non-magnetic and electrically conductive, as described herein.
  • An example ablation technique is laser cutting.
  • An example of a suitable laser technique uses parameters as shown in TABLE A.
  • the iron group binder metal is present in the substrate in an amount of less than about 0.5 wt-%, including up to being free of binder metal, there is an absence of recast material from the substrate in the region of the cut, for example in the kerf.
  • This is a huge cost in labor and equipment and consumes the benefit of speed achieved with laser cutting vice traditional EDM.
  • EXAMPLE 1 Diamond powder (6 micron grain size) was blended with 6 micron Fe and Ni (31 % Ni; carbon-saturated melting point 1254 Q C) powders and positioned on top of a 1 inch square x 0.140 inch metal-free carbide support.
  • the metal-free carbide support was obtained from North American Carbide, Buffalo, New York, and is a hot-pressed, WC body with about 0.4 wt-% cobalt metal.
  • the support is non-magnetic, due to low or no cobalt present, and conductive, due to the presence of WC.
  • the blended powder on metal-free carbide was placed within a conventional PCD support comprising conventional carbide support.
  • FIG. 3 shows a schematic of the arrangement, including the metal-free carbide support 20, the conventional carbide 22 and the blended powder 24.
  • the assembly was sintered in a conventional high pressure/high temperature (HPHT) arrangement at about 1450 Q C (melting point of cobalt catalyst in
  • the formed PCD cutting element was cut out of the PCD blank and ground on all sides to reveal the metal-free carbide substrate and PCD layer bonded to it.
  • the formed cutting element had good integrity and was not cracked; indicating that the coefficient of thermal expansion, adhesion, bend strength, impact toughness and heat-tolerance of metal-free carbide is compatible with PCD.
  • the coefficient of thermal expansion of metal-free carbide is about 4.5 ppm/K while the coefficient of thermal expansion of conventional carbide with about 13 wt-% Co is about 7.5 ppm/K, the coefficient of thermal expansion of cBN, diamond and B4C is about 3 ppm/K, the coefficient of thermal expansion of PCD is about 5.5 ppm/K, the coefficient of thermal expansion of PCBN is about 5 ppm/K, and the coefficient of thermal expansion of Co is about 12 ppm/K.
  • Table 1 shows the element analysis (XRF) of the PCD layer above the metal-free carbide, above conventional carbide, and of the metal-free carbide after sintering.
  • Melt cobalt catalyst has infiltrated from the conventional carbide into the metal-free carbide and into the PCD layer, displacing melt Fe and Ni. Furthermore, Fe and Ni from the diamond layer infiltrated the metal-free carbide. There is no change in the cobalt content of metal-free carbide before and after sintering. This is an indication that metal-free carbide (WC) is porous, attracts melt FeNi much more than cobalt, and attracts melt FeNi more than diamond.
  • WC metal-free carbide
  • the resulting blank was conductive and EDM cut to form a cutting tool edge.
  • the blank was laser cut at >300 mm 2 /min with no issue with recast metal.
  • the laser was as described above. There was a small amount of metal from the PCD layer cast on the edge that could be wiped off with an abrasive cloth. Grit blasting was not required. There was no chipping and minimal heat-affected-zone due to recast metal.
  • EXAMPLE 3 The part from Example 1 was placed in boiling 6M HCI acid for one hour to dissolve the catalyst metal from the PCD. The leached part was non- conductive and had ⁇ 0.5 wt-% metal based on XRF (see Table 2). Completely removing the metal did not delaminate the metal-free carbide from the PCD nor generate new defects in the PCD nor destroy the metal-free carbide substrate. The piece was laser cut at high speed >350 mm 2 /min with no recast metal. [0037] TAB LE 2:
  • catalyst metal can be removed by, for example, leaching for a suitable shorter time period, as disclosed, for example, in U.S. Patent No. 4,224,380, the entire contents of which are incorporated herein by reference.
  • EXAMPLE 4 The sandwich arrangement of Example 2 was repeated with 0.080" of conventional carbide and 0.060" of metal-free carbide around the same 6 micron diamond powder. It was sealed and sintered in the identical HPHT process. The sintered blank delaminated in several places within the PCD layer indicating this arrangement is unfavorable for supplying melt catalyst to the diamond layer due to the coefficient of thermal expansion of carbide and thickness of the carbide catalyst layer.
  • a formed cutting element consistent with that produced in Example 1 and having a PCD layer thickness of 1 mm and a substrate thickness of 3.5 mm was laser cut using the above laser parameters.
  • the cut rate of the laser cutting was in excess of 200 mm 2 /min, which was the maximum for the equipment. It was estimated that the maximum cut rate is approximately 300 mm 2 /min to approximately 400 mm 2 /min.
  • FIG. 4 is an image of a cross-section of the cutting element showing the cut surface where the substrate 12 and layer 14 have been sectioned by a laser. Note that at the substrate there is no recast metal. There is some recast metal 26 above the PCD, but this arises from the binder in the PCD layer, which was 13 wt-% Co.
  • FIG. 5 is an SEM micrograph at 1 ,50OX magnification of the region of the bond between a superhard material and a metal-free carbide substrate on which the superhard material is supported.
  • the adhesion between metal-free carbide substrate 30 and PCD 32 is made by catalyst Co 34 from the PCD layer interacting with the carbide forming a carbon-carbide liquid-phase sintered solid-state bond.
  • the bond strength persists.
  • FIG. 6 is a top view image of a conventional carbide that includes a binder metal, in this case Co 13 wt-%.
  • the sample 40 was laser cut using the identical parameters as in Example 1 .
  • a dense metal refill 44 due to the metal from the substrate recasting into the cut.
  • Above the cut there is a stacked feature of slag. Separation of the carbide did not occur as the recast metal effectively rewelded the parts together as the laser traversed.
  • Fig. 7 shows a cross-section of metal-free carbide laser cut at identical conditions revealing a clean cut edge with no recast metal.
  • the cut in the comparative example requires substantial post-cut processing, including removal of the stacked feature of slag, e.g., by grit blasting, and, once the section is separated, a cleaning operation on the cut surfaces themselves, e.g., grinding or blasting

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Earth Drilling (AREA)
  • Powder Metallurgy (AREA)
  • Magnetic Heads (AREA)
PCT/US2010/043197 2009-07-24 2010-07-26 Metal-free supported polycrystalline diamond (pcd) and method to form WO2011011771A2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP10738117.0A EP2456946B1 (en) 2009-07-24 2010-07-26 Supported pcd and manufacturing method thereof using low binder wc-substrate
KR1020127004748A KR101741282B1 (ko) 2009-07-24 2010-07-26 지지된 pcd 및 바인더가 없는 wc 기재를 사용한 제조 방법
JP2012521870A JP6038652B2 (ja) 2009-07-24 2010-07-26 金属不含担持多結晶ダイアモンド(pcd)及び形成方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US22819409P 2009-07-24 2009-07-24
US61/228,194 2009-07-24

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WO2011011771A2 true WO2011011771A2 (en) 2011-01-27
WO2011011771A3 WO2011011771A3 (en) 2011-06-23

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US (1) US8651204B2 (ko)
EP (1) EP2456946B1 (ko)
JP (1) JP6038652B2 (ko)
KR (1) KR101741282B1 (ko)
WO (1) WO2011011771A2 (ko)

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US20110017520A1 (en) * 2009-07-24 2011-01-27 Diamond Innovations, Inc. Metal-free supported polycrystalline diamond and method to form
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US20110017520A1 (en) * 2009-07-24 2011-01-27 Diamond Innovations, Inc. Metal-free supported polycrystalline diamond and method to form
US8651204B2 (en) * 2009-07-24 2014-02-18 Diamond Innovations, Inc Metal-free supported polycrystalline diamond and method to form
CN103273066A (zh) * 2013-05-20 2013-09-04 江苏锋泰钻石工具制造有限公司 金刚石切磨片的制备方法
CN103722174A (zh) * 2013-12-30 2014-04-16 中原工学院 一种自锐性聚晶金刚石复合片及其制备方法

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KR101741282B1 (ko) 2017-05-29
EP2456946A2 (en) 2012-05-30
KR20120039731A (ko) 2012-04-25
JP6038652B2 (ja) 2016-12-07
US20110017520A1 (en) 2011-01-27
US8651204B2 (en) 2014-02-18
WO2011011771A3 (en) 2011-06-23
EP2456946B1 (en) 2020-04-29

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